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United States Patent |
5,190,985
|
Mader
|
March 2, 1993
|
Stable aminoplast cellular foams and the process for their manufacture
Abstract
Stable, emission-free, low-shrinkage, fireproof aminoplastic cellular foams
are obtained by using an unsaturated, halogenated polyalcohol in the resin
precondensate constituent and a dodecylbenzolsulphonic acid partially
esterified preferably with a fatty alcohol and a long-chain polyhydric
alcohol, preferably a polyethylene glycol, in the foaming agent hardener
consituent. The foams are particularly suitable for building construction
and for covering, as well as in the agricultural sector and or oil
absorption. For certain of these applications, the resin pre-condensate
constituent of the invention can be processed with a conventional foamer
hardener constituent or the foamer hardener constituent of the invention
can be processed with a conventional resin precondensate constituent.
Inventors:
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Mader; Karl J. (Pfaffikon, CH)
|
Assignee:
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IDC System AG (Freienbach, CH)
|
Appl. No.:
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768990 |
Filed:
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January 21, 1992 |
PCT Filed:
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March 18, 1991
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PCT NO:
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PCT/CH91/00061
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371 Date:
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January 21, 1992
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102(e) Date:
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January 21, 1992
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PCT PUB.NO.:
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WO91/14731 |
PCT PUB. Date:
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October 3, 1991 |
Foreign Application Priority Data
Current U.S. Class: |
521/116; 521/88; 521/89; 521/97; 521/117; 521/121; 521/130; 521/187; 521/188 |
Intern'l Class: |
C08J 009/00; C08J 009/02 |
Field of Search: |
521/121,117,130,116,187,188,88,89,97
|
References Cited
U.S. Patent Documents
2542471 | Feb., 1951 | Brandon.
| |
3919166 | Nov., 1975 | Brachman.
| |
4225680 | Sep., 1980 | Williams | 521/188.
|
4390643 | Jun., 1983 | Kanada et al. | 521/188.
|
4511678 | Apr., 1985 | Mahnke et al. | 521/188.
|
4537913 | Aug., 1985 | Baumann | 521/188.
|
Foreign Patent Documents |
1054232 | Apr., 1959 | DE.
| |
2542471 | Mar., 1979 | DE.
| |
3216897 | Nov., 1983 | DE.
| |
584104 | Jan., 1977 | CH.
| |
1090816 | Dec., 1967 | GB.
| |
1470953 | Apr., 1977 | GB.
| |
Other References
International Search Report for PCT/CH91/00061 (WO91/14731).
|
Primary Examiner: Foelak; Morton
Attorney, Agent or Firm: Rothwell, Figg, Ernst & Kurz
Claims
I claim:
1. A stable aminoplastic cellular foam comprising a reaction product of an
amine formaldehyde precondensate constituent (A) with a foaming agent
hardener constituent (B) wherein constituent (A) contains a halogenated
alkene polyalcohol and/or constituent (B) contains dodecylbenzolsulphonic
acid, optionally partially esterified with a fatty alcohol, and contains a
long-chain polyalcohol.
2. Foam according to claim 1 wherein constituent (A) contains
2,3-dibromide-2-butene-1,4-diol.
3. Foam according to claim 1 wherein constituent (B) contains one or more
esters of dodecylbenzolsulphonic acid with C.sub.15 -C.sub.22 -fatty
alcohol.
4. Foam according to claim 2 wherein constituent (B) contains one or more
esters of dodecylbenzolsulphonic acid with C.sub.15 -C.sub.22 -fatty
alcohol.
5. Foam according to claim 1 wherein constituent (B) contains polyethylene
glycol.
6. Foam according to claim 2 wherein constituent (B) contains polyethylene
glycol.
7. Foam according to claim 3 wherein constituent (B) contains polyethylene
glycol.
8. A process for manufacturing a stable aminoplastic cellular foam
comprising reacting an amine formaldehyde condensate constituent (A) with
a foaming agent hardener constituent (B), wherein constituent (A) contains
a halogenated alkene polyalcohol and/or constituent (B) contains
dodecylbenzolsulphonic acid, optionally partially esterified with a fatty
alcohol, and contains a long-chain polyalcohol.
9. An aminoplastic precondensate constituent for manufacturing an
emission-free, fireproof foam by conversion with a foaming agent hardener
constituent, wherein the aminoplastic precondensate contains a halogenated
alkene polyalcohol.
10. A precondensate constituent according to claim 9 containing
2,3-dibromide-2-butene-1,4-diol.
11. A method of sound and/or heat insulating building construction
comprising filling the construction with an emission-free, fireproof, low
shrinkage, stable aminoplastic cellular foam comprising a reaction product
of an amine formaldehyde precondensate constituent containing a
halogenated alkene polyalcohol with a foaming agent hardener constituent.
12. A method according to claim 11 comprising filling the building
construction with a foaming agent hardener constituent containing
dodecylbenzolsulphonic acid, optionally partially esterified with a fatty
alcohol, and containing a long-chain polyalcohol.
13. A method according to claim 12 comprising filling the building
construction with a foaming agent hardener constituent containing
dodecylbenzolsulphonic acid, optionally partially esterified with a
C.sub.15 -C.sub.22 -fatty alcohol.
14. A method according to claim 13 comprising filling the building
construction with a foaming agent hardener constituent containing
polyethylene glycol.
15. A method of absorbing oil comprising applying a stable aminoplastic
cellular foam comprising a reaction product of an amine formaldehyde
precondensate constituent with a foaming agent hardener constituent
containing dodecylbenzolsulphonic acid and a long-chain polyalcohol.
16. A method of covering agricultural or dumping grounds comprising
applying stable aminoplastic cellular foams comprising a reaction product
of an amine formaldehyde precondensate constituent with a foaming agent
hardener constituent containing dodecylbenzolsulphonic acid and a
long-chain polyalcohol.
Description
The invention relates to stable, shrinkage-free, possibly fireproof and/or
emission-free aminoplastic cellular foams and the process for
manufacturing them from carbamide-formaldehyde resin condensate
(subsequently referred to as "amino resin precondensate") and a hardener
foaming agent as well as amino resin precondensate constituents and
hardener foaming agent constituents for manufacturing such foams.
Aminoplastic resin cellular foams have been in use for decades. However,
the use of these cellular foams as, for example, filling material for
hollow space in building construction, has been limited thus far due to
their instability, heavy shrinkage and undesirable emission of
formaldehyde. This is primarily because it has not been possible to
transfer the laboratory results achieved thus far to the work site (see,
for example, DIN 18159, Part 2, where 4% shrinkage is tolerated). In
addition, the conditions for shrinkage, related to the release of
formaldehyde, have been unsatisfactorily resolved. Therefore in recent
years aminoplastic cellular foams in building construction have been
almost totally driven from the market.
As of today polyhydric alcohols, such as, for example, polyethylene glycol,
diethylene glycol, sorbitol, etc. are state of the art additives to the
resin precondensate solution (see, for example, DE-PS 1.054.232, U.S. Pat.
No. 2,542,471). The use of these, presumably molecule chain stabilizing
alcohols, is limited by the constituent amounts. A surplus of alcohols
reduces the fireproof capability of the foams. In order to maintain this
fireproof capability nevertheless, ortho-boric acid transformation
products, for example, were added to alcohol surpluses as a counter
measure.
By adding boric acid esters it was possible to improve the resin quality or
cellular foam quality, but the products were still not completely
satisfactory (DE-PS 2.542.471).
Also proposed as formaldehyde binding for the manufacture of
low-formaldehyde products is the introduction into the foaming agent of
carbamide in concentrated form (DE-PS 32 16 897). Resorcinol is also used
for this purpose in the conventional foaming agent solutions. In addition,
phosphoric acid is used as a resin (DE-PS 32 16 897).
One object of the invention under consideration is the creation of
aminoplastic cellular foams with optimal stability with large volume and
low weight. An additional task of the invention under consideration is the
creation of low-shrinkage and/or emission-free aminoplastic cellular
foams.
The term "stable" refers, in relation to the invention under consideration,
to the foam's ability to resist decomposition.
The term "low-shrinkage" means in this case a linear shrinkage, at wood
industry standard conditions, of less than 4%, preferably of less than 1%
and generally preferred of, at the most, 0,2%.
By "emission-free" the understanding here is of foams that exhibit no
detectable smell of formaldehyde during and after hardening.
These objects will be accomplished in accordance with the invention by the
composition of the foaming agent hardener constituent on the one hand,
and/or the resin precondensate constituents on the other. The aminoplastic
cellular foams according to the invention and the process for
manufacturing them as well as the foaming agent hardener constituents and
resin precondensate constituents for manufacturing such foams are defined
in the independent claims. Preferred embodiment foams are to be found in
the dependent claims.
For the manufacture of emission-free, low-shrinkage, fireproof aminoplastic
cellular foams used for the most part as sound and heat insulation in
building construction, although for other purposes as well, a
halogen--(preferably bromide)--alkylene-polyol, for example
1,4-dibromide-2-butene-1,4-diol, is added to the resin precondensate
solution along with common polyhydric alcohols. The alkylene group of
these polyols includes unsaturated olefine groups with one or more double
bonds. Although the reaction mechanism has not been completely explained,
it is assumed that these compounds bind with the available free
formaldehyde as well as with the available methylol groups, that can
convert to formaldehyde, and produce stable compounds at both high and low
temperatures environments.
Along with the foam's low level of inflammability (corresponding to the
specifications of Swiss Fire Class V/3) brought about by the halogen
compound, aminoplastic cellular foams of historically unknown stability
can be achieved with this additive. Proteolytic reactions as a result of
external physical influences on the final hardened foam are completely
eliminated under normal conditions.
The products suitable as aminoplastic precondensate solutions are those
manufactured by conventional means, and obtained by conversion from
carbamide and formaldehyde in a mol-relation 1:1.25 to 1:2.5, preferred
1:2, at about pH 4 to 6 in about 30 to 70% water solution. Resin
precondensates obtained with a content of approximately 30 to 40
percentage by weight solids are preferable. These kinds of products can be
obtained commercially or easily manufactured by conventional means.
These resin precondensate constituents extended with additives in
accordance with the invention can be converted in a conventional manner
with a known, commercial foaming agent hardener constituent, or with the
foaming agent hardener constituent, according to the invention and
described below, and conventionally processed to a foam.
When, on the other hand, fire resistance does not play a large role and
shrinkage is unimportant, as, for example, when using the foaming agent
for covering or for oil absorption, commercial carbamides formaldehyde
precondensates can be converted with the foaming agent hardeners that are
in accordance with the invention.
It is, however, desirable or necessary to keep the shrinkage during
hardening to a minimum, as is the case, for example, in building
construction, and surprisingly it was discovered that completely
unexpected results are achieved when using a foaming agent solution based
on dodecylbenzolsulphonic acid, which, if necessary, is partially
esterified with one or more fatty alcohols, for example, a polyethylene
glycol. In this case molecule chain stabilizing and therefore shrinkage
reducing effects were recorded. A better surface distribution of the water
and an optimal foam cell structure with simultaneous omission of foam
volume loss occurred. The intensity of the foam can be optimally
controlled as desired by the degree of the esterification of the sulfonic
acid. Fatty alcohols with 15 to 22 carbon atoms are most suitable for
esterification.
Many inorganic and organic acids, as they are known among specialists, make
for suitable hardeners. It is best to use 85%, hydrous phosphoric acid
requiring only a portion of the former standard amounts. The inorganic
acid portion for hardening consists only 1/4 to 1/3 of the established
amounts necessary for the hardening of aminoplastic resin until now. The
surface tension of the foaming agent can be selectively influenced by the
amount of applied polyethylene glycol.
Polyethylene glycol is an additional factor in the construction of the foam
structure and acts simultaneously as a shrinkage reducer in the relatively
smallest proportional parts. Polyethylene of different molecular weights
can be used depending upon requirements.
The foaming agents obtained according to the invention are appropriate for
many uses, as packing material in building construction, in agriculture,
where the foaming agents have an advantage in the working environment, as
covering foams, where due to its stability a thin layer of foam results in
the desired sealing quality, as well as oil absorption, particularly crude
oil absorption and the like. They are biologically degradable. Because
they are almost completely porous, excellent oil absorption can be
achieved within an extremely short time, which is of the highest advantage
for oil spills of every kind.
The mixing and foaming of components A and B and the shaping and final
reduction of the foam can be achieved using conventional methods.
Advantageous is the use of a device according to CH-PS 584.104.
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Example 1: Foaming agent hardener solution
______________________________________
970 parts by weight
Water
18 parts by weight
Dodecylbenzolsulphonic acid
6 parts by weight
Phosphoric acid 85%
6 parts by weight
Polyethylene glycol
1,5 parts by weight
Resorcin
______________________________________
are processed to a homogenous solution.
This solution is suitable for the manufacture of an aminoplastic cellular
foam with a very stable foam structure by the addition of a commercial
aminoplastic precondensate solution (BASF), for example, in a facility as
described in the CH-PS 584.104. The biologically degradable foam obtained
in such a way is perfectly suitable for oil absorption, as a cover for
dumping grounds and in agriculture.
EXAMPLE 2
Foaming Agent Hardener Solution
The quality constancy and the stability of the foam can be improved further
if the constituent 1.5 parts by weight named in example 1 are given a
C.sub.15 -C.sub.22 -fatty alcohol that esterifies with one part of the
dodecylbenzolsulphonic acid. Processed with known amino-resin
precondensates or a solution according to example 3 they are suitable for
building construction and provide high stability as well as being
shrinkage-free and odorless.
EXAMPLE 3
Resin Solution
80 to 82 parts by weight of a commercial 37 to 40% aminoplastic
precondensate solution (BASF) are mixed with 10 parts by weight sorbitol
and 8 to 10 parts by weight 1,4-dibromide butene diol.
EXAMPLE 4
Aminoplastic Foaming Agent
In a facility according to CH-PS 584.104 the solutions obtained in example
2 and example 3 were processed in a ratio of 1:2 to 1:3 to a fireproof
foam that displays the following characteristics.
Four different samples (100.times.100.times.100 mm) were taken after the
foam (14 to 18 kg/m.sup.3) had been dried. These samples were subjected to
climate control for 24 hours before the examination at 50 per cent by
volume humidity. Then they were therm-stabilized in an oven (3 hours at
about 80.degree. C. over a steam bath). After these three hours the
samples were taken from the oven and dried for 24 hours in a climate
controlled room at 50 percent by volume humidity.
The mean weight loss of the four samples was 0,425 g per sample.
The mean linear mass loss per side of the cube was 1,58 mm.
An amino-resin foam of superior quality yields in practice under normal,
physical conditions a linear shrinkage of at the most 0.2%. The moisture
released during the drying phase contained on practical application only
traces of formaldehyde, that are physiologically no longer perceptible.
After subsequent drying the foam body remains stable and subsequently
delivers no formaldehyde, as occurs with the more conventionally known
foams.
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